Oxyalkylated derivatives of furfural-substituted phenol resins



Patented Mar. 11, 1952 UNITED STATES PATENT OFFICE OXYALKYLATED DERIVATIVES F. FUR- FUR-AL-SUBST-ITUTED PHENOL masms Melvin De Groote, University City, and Bernhard Keiseig web'ster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application January's 1950,

Serial No. 137,295

Claims. (01. 260-53) The present invention is concerned with certain new 'chemical products, compounds, or compositions having useful "application in various arts.

This :application is a continuation-in-part of our co-p'ending application Serial "No."8723,'filed February 16, 1948, now Patent 23991366, granted March 7,4950. Also see our co-pending application Serial No. 74,474, filed February'3, 1949. It includes methods or procedures for manufacturing said new chemical products, compounds-"or compositions themselves.

Said new compositions are hydrophile hydroxylated synthetic products; said-hydrophile (A) An alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycine and methylglyc'ide; and I (B) An oxyalkylation susceptible,:fusible, organic solvent soluble, watereinsolublefphenolsfur- .furalresin; said-resin being derived by reaction between a difunctional monohydric .phenol and furfural; said resin being formed in the substan tial absence of trifunctional phenols; said phenol being of the formula:

in which R is ahydrocarbon radical having 'at least 4 and not more than 12 carbon atomsand substitutedinthe 2,4,6 position sai'd oxyalkylated resin being characterized by 'the'in'troduction into the resin molecule ofa plurality of divalent radicals having the formula (R)n' in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicala'butylene radicals, hydroxypropylene radicals, and hydrox-y- .butylene radicals, and n'is a .numeral varying from 1130 With, the 'pi'OV'isO that at'1east 2 moles or alkyl'ene oxidebe introduced "for each phenolicnucleus. p

.Although the herein described productshave a number of'indu'strial applications-,fthey are or particular Value 'foisrsolliiilg' pen-deem emulsynthetic products being oxyalkylation products 1 50 ileflelld 'aS required.

5 tergents-in the acid washing of building-stone and brick; as wettingagents and spreaders in'the application of'asphaltin road building and the like; 'as a flotation reagent in the flotation separation' of various aqueous suspensions containing 20 negatively charged particles such as sewage, coal washing waste'water, and various trade wastes and the like, asgermicides, insecticides, emulsitying agents, as, for example, for cosmetics, spray oils, water replle'nt textileifi'nishes, as' lubricants,

etc.

F oiipurpose of convenience, what is said here- .inafter :wm Ibe vdivided into two parts. Part 1 will be concerned with the production of the resin from a mixture of the kind specified and described in greater detail subsequently, and Part 2 will be concerned with oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative. V

PART-1 The production of resins from difunctional hydroicarbon-substituted-phenols is well 'knownand such 'resins are important in the art, particularlyin thepreparationof varnish and similar coatings. Those aderive'd from furfural=instead of formaldehyde, uifor example, have limitations in their use, due tothel fat that mailer i is apt to :g'ive-ia compound having afdark color. In an'y event, the production of 'such "resins is con've'ntional.

In the preparation of the resins and also in the subsequent oxyalkylation step described in Part Two, 'frequent'reference will "be made to a number of co-pending applications"for purpose pf soluble resin, semi-pliable to hard.

3 Example 1AA Grams Para-tertiary amylphenol 164 Furfural 96 Potassium carbonate 8 The equipment used was a conventional twopiece laboratory resin pot. The cover part of the equipment had four openings, one for reflux condenser, one for the stirring device, one for a separatory funnel or other means of adding reactants, and a thermometer well. The device was equipped with a combination reflux and water trap apparatus, so that the single piece of apparatus could be used as either a reflux condenser or a water trap, depending upon the position of the three-way glass stop-cock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve without disconnecting .maximum temperature during and after removal of water was approximately 205 C. The resin wasa reddish'black resin, xylene-soluble, and semi-soft to pliable in consistency.

See Example 90a of our co-pending application, Serial No. 8,723, filed February 16, 1948, or

Example 88a of Serial No. 74,474, filed February the equipment. The resin pot was heated with a glass fibre electrical heater constructed-to fit i H H snugly around the resin pot. Such heaters, with regulators, are readily available.

The furfural was shaken with dry sodium carbonate prior to use, to eliminate any acid, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Company, Chicago, Illinois.

The above reactants were heated under the reflux condenser for two hours in the same resin pot arrangement described above. As previously stated, the separatory funnel device was not employed. No xylene or other solvent was added. The amount of material vaporized and condensed was comparatively small, except for the water of reaction. At the end of this heating or reflux period the trap was set to remove the water. The

maximum temperature during and after removal of water was approximately 202 C. The material in the trap represented 16 cc. water and 1.5 cc. furfural. The resin was a bright black, hard resin, xylene-soluble, and had a melting point of 130 to 135 C., with some tendency towards being slowly curable. We have also successfully followed this same procedure, using 3.2 grams of potassium carbonate instead of 8.0 grams.

For purpose of comparison, see Example 42a in our co-pending application Serial No. 82,704, filed May 21, 1949, now Patent 2,499,370, granted March 7, 1950 in which the same designation, i; e., Example 42a, is again employed to identify the same example.

Example 2AA Grams Para-tertiary amylphenol 164 Furfural (conbonate treated) 70 Potassium carbonate 3.2

The procedure employed was the same as thatof Example 1AA, preceding. The amount of water distilled was 10 cc. and the amount of furfural 3 cc. The resin was bright black, xylene- See Example 43a in our co-pending application, Serial No. 82,704, filed May 21, 1949, in

- which the same designation, i. e., Example 43a,

is again employed to identify the same example.

Example 3AA Grams Ncnylphenol (1.0 mole) 220 Furfural (NazCOa treated) (1.0 mole) 96 Potassium carbonate 12. Xylene 200 Example 4AA Grams Menthylphenol (1.0 mole) 232 Furfural (NazCO3 treated) (1.0 mole) 96 ,Potassium carbonate 12 Xylene 200 Example 89a of Serial The procedure followed was the same as that in Example 1AA, preceding. The solvent-free resin was reddish black in color, hard, brittle, with a melting point of 158 to 163 C., and showed a definite tendency towards being heatcurable.

See Example 91a of our co-pending application, Serial No. 8,723, filled February 16, 1948, or No. 74,474, filed February Example 5AA The same procedure was followed as in Example 1AA, preceding, except that 206 parts by weight of commercial para-octylphenol replaced 164 parts by weight of para-tertiary amylphenol. In co-pending application Serial No. 74,474 this particular resin is indicated as Example 144a,

. and theresin previously referred to as Example 1AA is referred to as Example 42a.

Example 6AA The same procedure was followed as in Example lAA, preceding, except that 170 parts by weight of commercial para-phenylphenol replaced 164 parts by weight of para-tertiary amylphenol. In our co-pending application Serial No-.- 74,474, this resin was referred to as Example 149a, and Example 1AA was referred to as Example 42a.

Example 7AA Grams Para-tertiary butylphenol 150 "Eurfural -(NazCO3 treated) "I '96 Potassium carbonate 10 Xylene 200 v The procedure employed was the same as that in Example 1AA, preceding. The solvent-free resin was black or reddish black in color, xylenesoluble, hard and very brittle. Its melting point .Ezcample 8AA Example 9AA This resin was made in exactly the same way asExample 1AA, except that 164 parts by weight of para-tertiary amylphenol were replaced by 170 parts of commercial para-phenylphenol. The final product had substantially the same appearance, solubility characteristics, etc., has resin Example 1AA.

The resinification procedure previously described yields resins havingat least 3 phenolic nuclei and usually modestly in excess thereof. In other words, an average of 4, 5 or 5 or 6 nuclei per resin molecule.

As pointed out in our aforementioned co-pending application Serial No. 8,723, other means are available to yield resins in which there may be present a larger number of phenolic nuclei, for instance, 7 to 15. Such resins are conveniently obtained by subjecting the resin obtained in the conventional manner to further treatment under a vacuum at a temperature below the pyrolytic point of the resin. Sometimes the expression low-stage resin or low-stage intermediate is employed to mean a stage having 6 or 7 units or even less. In'the appended claims we have used low-stage to mean 3 to 7 units, based on average molecular weight.

PART 2 Example 1BB The resin employed was the one described under the heading of Example 1AA. 100 grams of the resin were mixed with 100 grams of xylene so as to give a 50% solution. 2% of sodium methylate, based on the solvent-free resin was added as a catalyst. The solution of the resin was placed in a small laboratory autoclave and the mixture reacted with 50 grams of ethylene oxide. During this addition the maximum temperature was 115 0., the maximum pressure was 104 pounds per square inch, and the time required to add the oxide was 2 hours. Needless to say, the mixture was stirred constantly during the reaction and the reaction considered at an end when there was no further drop in pressure, thus indicating that all the ethylene oxide present had reacted. The pressure registered on the gauge at the end of the reaction indicated the vapor pressure of xylene at the indicated temperature. As the end of this first addition there was no particular change in the solubility of the product, i. e., it was practically as insoluble as the original xylene solution of the resin. A second 50 grams of ethylene oxide were added in another 2-hour period. In this second addition the maximum temperature was 130 and the maximum pressure 95 pounds. At the end of this period the product began to show a definite tendency to emulsify.

A third 50-gram addition of ethylene oxide was then made during a one-hour period. In this particular addition the maximum temperature was 120 and the maximum pressure 96 pounds.

Theproductat the end of this 3-hour period was entirely water-soluble.

Example ZBB The same procedure was followed as in Example lBB, immediately preceding, except that the resin employed was that of Example 2AA, instead of 1AA. The two initial resins were very much alike and the conditions of addition were substantially the same, i. e., 150 grams of ethylene oxide added to 100 grams of resin in three periods of 2 hours, 2 hours and one hour. The conditions under which addition of ethylene oxide was made, as far as temperature and pressure are concerned, were substantially the same as in Example lBB, preceding. The amount of sodium methylate added was the same, and the solubility characteristics at the end of each period were substantially the same.

Example 333 The same reactants, and procedure were employed as in Example lBB, preceding, except that propylene oxide was employed instead of ethylene oxide. The resultant, even on the addition of the alkylene oxide in the weight proportions of the previous example, has diminished hydrophile properties, in comparison with the resultants of Example lBB. This illustrates the point that propylene oxide and butylene oxide give products of lower levels of hydrophile properties than does ethylene oxide.

Example 4BB The same reactants and procedure were followed as inExample lBB, preceding, except that.

Example 583 The same procedure was followed as in Example lBB, preceding, except that the resin employed was the one described under the heading of Example 7AA. The amount of resin used was grams, dissolved in 100 grams of xylene. 4 grams of sodium methylate were added, along with 100 grams of ethylene oxide. Due to the increased amount of catalyst the reaction time was somewhat more rapid than in Example 1AA, preceding. The reaction was complete in one-half hour. The maximum temperature employed was C., and the maximum pressure 150 pounds per square inch. At the end of this periodthe product showed some tendency to emulsify.

The second addition of 100 grams of ethylene oxide was then made. The time required was 1 hours, the maximum temperature was 150 0., and the maximum pressure pounds.

The product showed definite water-emulsifiability but was not water-soluble.

The third addition of ethylene oxide was made, using another 100 grams. The maximum temperature during this period was 162 C., and the maximum pressure 165 pounds. The time required was 2% hours. During this third period there was a definite tendency towards rubberiness and the product seemed to be only partially soluble in xylene. The product was solubilized by the addition of the diethylether of ethylene glycol. 150 grams of this solvent were aded. The product then was a deep amber-colored, somewhat viscous liquid, which was water-soluble.

Instead of preparing resins on a laboratory scale, we have also prepared phenol-furfural resins of the kind described, in a 10 to -gallon electro-vapor synthetic resin pilot plant reactor. Such piece of equipment is manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and is described completely in their Bulletin No. 2087, issued in 1947, with specific reference to specification No. 71,3965.

For convenience, the numbers given in the following tables are the same as the identical laboratory size batches previously described, and it is understood that they were simply stepped up in size, but otherwise made in the pilot plant equipment previously described.

The solvent used in each instance was xylene. This solvent is particularly satisfactory, for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 P... P. M.

Phenol for resin: Para-tertiary amylphenol Date, August 27-31, 1948 In the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, one-half to one gallon, one can proceed through the entire molal stage of one to one, to one to twenty, without remaking at any intermediate stage. However, in most cases, we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result, it was necessary in such instances to start with a new resin sample in order to prepare suflicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passe'd or ignored. This is illustrated in the tables, where, obviously, it shows that the starting mix was not removed from a previous sample. Such pilot plant size resin pot is adapted to operate under pressure; and provided the resin permits a working pressure of 200 pounds or thereabouts, resinification and oxyalkylation can take place in the same piece of equipment. We have repeatedly used equipment for this dual purpose.

In order to do what we have stated previously, i. e., preserve reference to our co-pending application Serial No. 74,474, filed February 3, 1949, we are presenting the same data which appears therein in verbatim form. adding only one thing to identify the resin in the instant case.

Aldehyde for resin: Furfural [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 420 but this batch designated as 1340,]

Mix at End of Starting Mix Reaction Resin 1AA Mix Which is Removed for Sample Mix Which Remains as Next Starter Max. Pres- Max. Tem- Time,

Lbs. Solvent Lbs. Solvent Lbs. Resin Lbs. EtO

Lbs. Resin Lbs. EtO

Lbs.

Lbs. Resin vent sure, lbs.

' Solubility sq. 1H.

peigauro, hm Lbs.

Soi-

vent

Lbs. EtO

Lbs. Resin Lbs. EtO

Er. 6BB

First Stage Resin to EtO Molal Ratio 1:l Ex. N0. 1341) Ex. 7BB

Second Stage Resin to EtO. Molal Ratio 1:5" Ex. No.135b

Er. BBB

Third Stage Resin to Eton... Molal Ratio 1:l0 Ex. No. 1365..."

Ex. EBB

Fourth Stage Resin to EtO Molal Ratio l:l5 Ex. No. 1437b...

Ex. IOBB Fifth Stage Resin to EtO..

Molal Ratio 1:20. Ex. No. 1138b 0.85 8.45 13.6 2.65 Not soluble.

7.55 3.42 5.48 5.10 110 Somewhat soluble.

7.90 2.05 3.65 6.60 163 Soluble.

.................. 180 188 Very soluble.

...................... M Very soluble.

Resin is 1AA. Reference to 42a and 134a is for comparison with Serial No. 74,474, filed Feb. 3, 1949. This is true also in regard to reference to Ex. 134b to 1380, inclusive. These 5 examples in the present case are, as noted, Examples 6BR through 1033, inclusive.

Phenol'for resin: Para-rtonylphenol Aldehydesfor resin: l lurfural Date, October 13-15, 1948 [Resin made on pilot plant size batch, approximately25 pounds, corresponding to 88:1 but this batch designated. as 154a].

. Mix Which is Mix Which Re- Starting Mix gg figg of Removed for mains as Next Sample. Starter Mex. P as Max. Tem- Resin 3AA I 1 Sol- Sol- Vent Resin EtO vent Resin EtO vent Resin EtO vent Resin EtO Time,

First Stage Resin to EtO Molal Ratio 1:1 10.85 20.75 10.85 20.75 3.0 2.57 4. 90 0.73 8.28 15.85 2.27 100 150 Pi Insoluble. Ex. No. 1540".-. l

E1. 12BB Second Stage Slight tend- Resln to EtO.- alloy to- Molal Ratio 1:5 8 28 15.85 2.27 8. 28 15.85 11.77 3.82 7.33 5.45 4.46 8.52 6.32 100 182 word he- Ex; No. 1551)-.. coming soluble. Er;18BB

Third Stage Resin to Eton...

Molal Ratio 1:10. Ex. No. 156b.

Fourth Stage Resin to'Et0.

11.35 5.95 11.35 16.75 3:38 6:42 9. 50 2.57 4.93 7.25 100 181 A:F%i1rly 5011b.

Molal Ratio 1:15. Ex. N0. 1570..."

Ex.15BB

Fifth Stage Resin to Et p 8.52 6.32 4.46 8.52 19.07 90 188 it Readily soluble:

4.93 7.25" 2.57 4.93 14.50 100 160 tgjq'uits soluhie.

Resin is 3AA. Referenee'to 88a and 1540 is for comparison with Serial N 0. 74,474, filed Feb. 3, 1949. This is true also in regard to reference to Ex. 154!) to 158b, inclusive. These examples 1n the present case are, as noted, Examples 1113B through 1513B, inclusive.

Phenol for resin: Il Ienthyi ph'enol Aid ehyde for resin: Furfurai. Date, September 23-24, 1948 [Resin made on pilot size batch, approximately pounds, corresponding to 89a, but this batch designated as 139a.]

, Mix Whieh is I Mix Which Refi 3 5 or Removed [or mains as Next Sample Starter Max. Pres- Max. Tem- Time Resin 4AA sure, lbs. peigaure, hm Solubility Lbs. Lbs. Lbs. Lbs. SOL Lbs Lbs SOL Lbs. Lbs. SOL Lbs. Lbs. Lbs. Lbs

Sol- Vent Resln EtO vent Resm EtO vent Resin EtO Vent Resin EtO I Starting Mix First Stage Resin to EtO I Molal Ratio 121.. 10.25 17. 10. 25 17. 75 2. 5 2. 65 4. 60 0.65 7. 6 13. 15 1.85 90 150 3 6 Not soluble. Ex.No.139b.

E1. 17BB Second Stage Resin to EtO Molal Ratio 1:5 7 6 Ex. No.140b

Er. 18BB Third Stage Resin t'o EtO Somewhat soluble Molal Ratio 1:10. Ex. No.14lb

6. 9S 4. 22 6.98 10.0 165 Soluble.

Molal Ratio 1115. Ex. No. 142!) 6. 24 3. 76 6. 24 13. 25 171 Pi Ver-y Soluble.

Ex. QOBB' Fifth Stage Resin to EtO Molal Ratio 1:20. 2 4

4.15 2.95 2.4 4.15 11.70 Ex.No.143b.

. 90 Very soluble.

. .Resin is 434.4. Reference to 89m and 13911 is for comparison with Serial No. 74,474, filed Feb. 3, 1949. This is true also in regardto reference to Ex. 139!) to 143h,'inclusivo. These 5 examples in the present ceseare, as noted, Examples 168B thru 2088, inclusive.

Phenel for resin: Para-octyl phenol Date, October 7-8, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, correspo replacing 164 parts by weight of para-tertiary am Aldehyde for resin: Furfural ndiug to 42a with 206 parts by weight of commercial para-octylphcnol ylphenol but this batch designated as 1440.]

Resin 8AA Starting Mix Mix at End Reaction Mix Which is Removed for Sample mains as Next Starter Mix Which Re- Max. Pres- Lbs. Solvent Lbs. Resin Lbs. EtO

Lbs. Solvent Lbs. Resin Lbs. EtO

Lbs. Solvent Lbs. Resin Lbs. EtO

Lbs. Solvent Lbs. Resin EtO sure, lbs. sq. in. s.

Max. Temperatnre, C.

Time, hrs.

Solubility Ex. 21 BB First Stage Resin to EtO Molal Ratio 1: Ex. No. 1445...

E1. .tZBB

Second Stage Resin to EtO Molal Ratio 1:5.. Ex. No. 145!) E1. .QSBB

Third Stage Resin to EtO Molal Ratio 1:10. Ex. No. 1460...

Ez. 248B Fourth Stage Resin to Et0 Molal Ratio 1:15. Ex. No. 1471;

Ex. .95BB Fifth Stage Resin to EtO Molal Ratio 1:20. Ex. No. 1485.

Insoluble.

Slight tende n c y t o ward bee o m i n g soluble.

M Fairly soluble.

4 Readily soluble.

M Quite soluble.

Resin is 8AA. Reference to 42a and 144a is for comparison with Serial No. 74,474, filed Feb. 3, 1949. This is true also in regard to reference to Ex. 1445 through 1485, inclusive. These 5 examples in the present case are, as noted, Examples 21BB thru 2513B, inclusive.

Phenol for resin: Para-phenyl phenol Date, October 11-13, 1948 [Resin made on pilot plant size batch, approximately 25 polmds, correspon replacing 164 parts by weight of para-tertiary am Aldehyde for resin: Furfural ding to 42a with 170 parts by weight of commercial paraphenylpheno ylphenol but this batch designated as 149m] Resin 9AA Starting Mix Mix at End of Reaction Mix Which is Removed for Sample mains as Next Starter Mix Which Re- Max. Pres- Lbs. Solvent Lbs. Resin Lbs. EtO

Lbs.

Lbs. Lbs

Resin Etd vent v Lbs. Sol- Lbs. ent Resin Lbs. EtO

Lbs. Solvent Lbs. Resin Lbs. EtO

sure, lbs. sq. in.

Max. T emperature, C.

Time, hrs.

Solubility Er. 6BB

First Stage Resin to Et0.--. Molal Ratio 1:1 Ex. No. 1490..."

E2. 27BB Second Stage Resin to EtO..... Molal Ratio 125.. Ex. No. 150b-- Third Stage Resin to EtO.. Molal Ratio 1:10. Ex. No. l5lb- Er. 298B Fourth Stage Resin to EtO1 Ex. No. 1525...

Ex. SOBB Fifth Stage .Resin to EtO- 2 EX. N0. 153b Sample somewhat rubbery and gelatinous but fairly soluble Insoluble.

Slight tendency toward solubility.

Fairly soluble.

l- Readily solublc.

Resin is 9AA. Reference to 42a and 149a is for comparison with Se to Ex. 1495 to 153b, inclusive. These 5 examples in the present case are,

rial No. 74,

as noted,

474, filed Feb. 3, 1949. This is also true in regard to reference Examples 26BB thru 3OBB, inclusive.

13 Attention isdirected to the fact thatthe -'resinsherein described must be fusible and soluble" ina non-polar solvent; such as xylene; although obviously, they-may be-soluble and usually'are', in

other polar or oxygenated solvents; aspreviously noted. Fusible resins invariably are soluble in one or more organic solvents, such as thosemenktioned elsewhere'herein. It is to be emphasized, however, that the organic solvent employedto-indicate or assure that the resin meets this requirement need not be the 'oneused'in oxyalkylation. Indeed, requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are includedin this group of organic solvents. Examples or such solvents are alcohols and alcohol ether's; However, where a'resin iss'oluble in an organic solv ent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent soluble resin can be finely powdered, forinstance, to 100 to zoojmesh, and'a' slurry'or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is so1ub1e man'organic'sowent; or the fact that it isfusible, means that it consists of separate molecules. Phenol-aldehyde resins of'the type herein specified possess reactive hydroxyl groups and are oxyalkylation-susceptible.

Considerable of what is saidimmediatelyhereinafter is concerned with theability to vary the hydrophile properties of the compounds used in the process from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, and equally difficult to explain, are the versatility and utilityiof thesecom'poun'dsas one goes from minimum hydrophile" property to ultimate maximum hydrophile property. Formstance, minimum hydrophile property may be described roughly as the point where'tvvo ethyleneoxy radicals or moderately ine'xcessthereof are introduced per phenolic hydroxyl. Such" minimum hydrophile property or sub-surfaceactivity'or'minimum surface-activity means'that the product shows at least emulsifyingprope'rti'es or self-dispersion in cold or evenin warm distilled water to 40 C.) inconcentrationsof 035% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes lf one continues to shake a hot solution, even through cloudy or containing an insoluble phase, one finds that solution takes place to give a'homogeneous phase as the mixture cools. Such self-dispersiontests' are'conducted in theabsence of an insoluble solvent.

When the hydrophile-hydr'ophobe balance is above the indicated minimum zmolesofethylene oxide per phenolic nucleusor th'eequivalent) but insuflicient to give a sol as described immedi ately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by'having present 10 to of an inert solvent such as xylene; All that one need to do" is: to have a xylene solution within the range of 50 to 90 parts-by'weight of oxyalkylated derivatives and 50"to 10 partsby weightof xylene and mix such solution with one, twoo'r' three times its volume'of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil i'r'i-wat'er type or the water-'in oil' type (usually the former) but,

any event, isdue tothe hydrophile-hydrophobe' balance of the oxy-alkylatedderivative. we refer simply to use the xylene diluted derivatives, which are described elsewhere, forthis' test rather than evaporate the solvent and employanymore elaborate tests, if the solubility is not suflicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethyleneglycol diethylether, with a little acetone added if required, making a rather concentrated solution, for'instance 40%to 50%, and then adding enough of" the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0%" strength solution. If the product is selfdispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable) such 501 or dispersion is referredto as at least semistable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they'remain at least for some period of time, forinst'ance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.). Needless to say, a test can be'made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surfaceactivity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lowerand intermediate stages of oxyalkylation.

Allowance must be made for the presence ofa solvent in the" final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as demulsifying agents, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extentthat they have emulsifying properties or are selfemulsifying; that is; when shaken with water they produce stable or semi-stable suspensions, or, in the presence ofa water-insoluble solvent, such as xylen'e, an emulsion; In demul sification, itissometimes preferableto usea product-having markedly enhanced hydrophile properties over andabove the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efficaciousresults are obtained with products-which do not have hydrophile'prope-rties' beyond the stage'of self -dispersibility.

More highly oxyallzyiated resins give colloidal solutions-or sols which show typical properties comparable to ordinary surface-activeagents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined'in this samemann'er but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface a'ctive emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylenewater emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vi orously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-inxylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsiflcation begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsiiy an insoluble solvent such as xylene. It

is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as ,to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature of structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. Hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, waterinsoluble, low-stage phenol-furfural resin; said resin being derived by reaction between a difunctional monohydric phenol and furfural under alkaline conditions; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent 17 furfural resin; said resin being derived by reaction between a difunctional monohydric phenol and furfural under alkaline conditions; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)11.; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with 18 the final proviso that the hydrophile properties of said oxyethylated resin in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously'with one to three volumes of water.

3. The product of claim 2, wherein R is an amyl radical.

4. The product of claim 2, wherein R. is an octyl radical.

5. The product of claim 2, wherein R is a nonyl radical.

MELVIN DE GROOTE. BERNI-IARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,501,015 Wirtel Mar. 21, 1950 

1. HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, LOW-STAGE PHENOL-FURFURAL RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND FURFURAL UNDER ALKALINE CONDITIONS; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA: 